Ultra-stable lamellar mesoporous silica compositions and process for the preparation thereof

ABSTRACT

Novel lamellar mesoporous silica compositions which can contain functional inorganic elements and organic functional groups as part of the lamellar silica framework structure are described. The compositions are prepared using gemini amine surfactants as templates or structure directing agents. The compositions have novel high temperature and hydrothermal stability and unique fundamental particle structures.

This application is a divisional application Ser. No. 09/436,839 filedon Nov. 9, 1999 now U.S. Pat. No. 6,528,034

GOVERNMENT RIGHTS

This invention was funded by the National Science Foundation (NSFCHE-96-33798 and CHE-99-03706). The U.S. Government has certain rightsin this invention.

FIELD OF THE INVENTION

The present invention relates to novel mesoporous, lamellar silicacompositions and to a method for the preparation thereof. In particularthe present invention relates to the use of novel gemini aminesurfactants as templating or structure directing agents.

DESCRIPTION OF RELATED ART

Porous materials created by nature or by synthetic design have foundgreat utility in all aspects of human activity. The pore structure ofthe solids is usually formed in the stages of crystallization orsubsequent treatment. Depending on their predominant pore size, thesolid materials are classified as: (i) microporous, having pore sizes<20 Å; (ii) macroporous, with pore sizes exceeding 500 Å; and (iii)mesoporous, with intermediate pore sizes between 20 and 500 Å. The useof macroporous solids as adsorbents and catalysts is relatively limiteddue to their low surface area and large non-uniform pores. Microporousand mesoporous solids, however are widely used in adsorption, separationtechnology and catalysis.

Owing to the need for higher accessible surface area and pore volume forefficient chemical processes, there is a growing demand for new, highlystable mesoporous materials. Porous materials can be structurallyamorphous, paracrystalline, or crystalline. Amorphous materials, such assilica gel or alumina gel, do not possess long range order, whereasparacrystalline solids, such as γ- or η-Al₂O₃ are quasiordered asevidenced by the broad peaks on the x-ray diffraction patterns. Bothclasses of materials exhibit a broad distribution of pores predominantlyin the mesoporous range. This wide pore size distribution limits theshape selectivity and the effectiveness of the adsorbents, ion-exchangesand catalysts prepared from amorphous and paracrystalline solids.

Hereafter, in order to clarify one of the objects of the presentinvention, the terms framework-confined uniform porosity and texturalporosity are defined and differentiated. Framework-confined uniformpores are pores formed by nucleation and crystallization of theframework elementary particles. These pores typically are cavities andchannels confined by the solid framework. The size of the cavities andchannels, i.e. the size of the framework-confined uniform pores, inmolecular sieve materials is highly regular and predetermined by thethermodynamically favored assembly routes. The framework-confined poresof freshly crystallized product are usually occupied by the templatecations and water molecules. While water molecules are easily removed byheating and evacuation the ionic templating materials, such asquaternary ammonium cations, due to their high charge density, arestrongly bonded or confined to the pore cavities and channels of thenegatively charged framework. The same concepts are expected to applyfor the charge reversed situation where an anionic template is confinedin the pores of a positively-charged framework. Therefore, a cation oranion donor or ion pairs are necessary in order to remove the chargedtemplate from the framework of the prior art molecular sieves.

Textural porosity is the porosity that can be attributed to voids andchannels between elementary particles or aggregates of such particles(grains) Each of these elementary particles in the case of molecularsieves is composed of certain number of framework unit cells orframework-confined uniform pores. The textural porosity is usuallyformed in the stages of crystal growth and segregation or subsequentthermal treatment or by acid leaching. The size of the textural pores isdetermined by the size, shape and the number of interfacial contacts ofthese particles or aggregates. Thus, the size of the textural pores isusually at least one or two orders of magnitude larger than that of theframework-confined pores. For example, the smaller the particle size,the larger the number of particle contacts, the smaller the texturalpore size and vice versa. One skilled in the art of transmissionelectron spectroscopy (TEM) could determine the existence offramework-confined micropores from High Resolution TEM (HRTEM) images orthat of framework-confined mesopores from TEM images obtained byobserving microtomed thin sections of the material as taught in U.S.Pat. No. 5,102,643.

One skilled in the art of adsorption could easily distinguish andevaluate framework-confined uniform micropores by their specificadsorption behavior. Such materials usually give a Langmuir type (TypeI) adsorption isotherm without a hysteresis loop (Sing et al., PureAppl. Chem. vol. 57, 603–619 (1985)). The existence of texturalmesoporosity can easily be determined by one skilled in the art of SEM,TEM and adsorption. The particle shape and size can readily beestablished by SEM and TEM and preliminary information concerningtextural porosity can also be derived. The most convenient way to detectand assess textural mesoporosity is to analyze the N₂ or Aradsorption-desorption isotherm of the solid material. Thus, theexistence of textural mesoporosity is usually evidenced by the presenceof a Type IV adsorption-desorption isotherm exhibiting well definedhysteresis loop in the region of relative pressures Pi/Po>0.4 (Sing etal., Pure Appl. Chem. 57 603–619 (1985)). This type of adsorptionbehavior is quite common for a large variety of paracrystallinematerials and pillared layered solids.

The only class of porous materials possessing rigorously uniform poresizes is that of zeolites and related molecular sieves. Zeolites aremicroporous highly crystalline aluminosilicates. Their lattice iscomposed by TO₄ tetrahedra (T=Al and Si) linked by sharing the apicaloxygen atoms. Oriented TO₄ tetrahedra, consists of cavities andconnecting windows of uniform size (Breck, D. W., Zeolite MolecularSieves: Structure, Chemistry and Use; Wiley and Sons; London (1974)).Because of their aluminosilicate composition and ability to discriminatesmall molecules, zeolites are considered as a subclass of molecularsieves. Molecular sieves are crystalline non-aluminosilicate frameworkmaterials in which Si and/or Al tetrahedral atoms of a zeolite latticeare substituted by other T atoms such as B, Ga, Ge, Ti, V, Fe, or P.

Zeolite frameworks are usually negatively charged due to the replacementof Si⁴⁺ by Al³⁺. In natural zeolites this charge is compensated byalkali or alkali earth cations such as Na⁺, K⁺ or Ca²⁺. In syntheticzeolites the charge can also be balanced by ammonium cations or protons.Synthetic zeolite and molecular sieves are prepared usually underhydrothermal conditions from aluminosilicate or phosphate gels. Theircrystallization, according to the hereafter discussed prior art, isaccomplished through prolonged reaction in an autoclave for 1–50 daysand, often times, in the presence of structure directing agents(templates). The proper selection of template is of extreme importancefor the preparation of a particular framework and pore network. A largevariety of organic molecules or assemblies of organic molecules with oneor more functional groups are known in the prior art to give more than85 different molecular sieve framework structures (Meier et al., Atlasof Zeolite Structure Types, Butterworth, London (1992)). An excellentreview of the use of various organic templates and their correspondingstructures, as well as the mechanism of structure directing is given forexample in Gies et al., Zeolites, vol. 12, 42–49 (1992). Due to theiruniform pore size, unique crystalline framework structure and abilityfor isomorphous substitution synthetic zeolites and molecular sieves areextremely suitable for a number of adsorption, separation and catalyticprocesses involving organic molecules. Recently, it has been discoveredthat synthetic zeolites and molecular sieves can be functionalized bypartially substituting the framework T-atoms with such metal atomscapable of performing different chemical (mostly catalytic) tasks. As aresult, a large variety of highly selective catalysts have been reportedduring the last decade. In the spectrum of molecular sieve catalyst aspecial place is occupied by the metal-substituted, high silicamolecular sieves (Si/Al ratio>5). Such molecular sieves are highlyhydrophobic and therefore exhibit high affinity toward organicmolecules. Among these important materials the microporousTi-substituted high silica molecular sieve, silicalite-1 (denoted TS-1),with MFI structure and pore size of ≈6 Å is quickly emerging as avaluable industrial catalyst due to its ability to oxidize organicmolecules at mild reaction conditions.

The microporous transition metal-substituted zeolites and molecularsieves of the prior art exhibit mainly framework-confined uniformmicropores, and little or no textural mesoporosity as evidenced by theirLangmuir type adsorption isotherms accompanied with poorly developedhysteresis loops at Pi/Po>0.4. The typical values for their specificsurface area are from 300–500 m²/g and for the total pore volume≦0.6cm³/g (Perspectives in Molecular Sieve Science, Eds. Flank, W. H. andWhite T. E. Jr., ACS symposium series No. 368, Washington D. C., p. 247;524; 544 (1988)). All known microporous high silica metallosilicates areprepared by prolonged crystallization at hydrothermal conditions, usingsingle quaternary ammonium cations or protonated primary, secondary ortertiary amines to assemble the anionic inorganic species into amicroporous framework. The use in the prior art of neutral amines andalcohols as templates (Gunnawardane et al., Zeolites, vol. 8, 127–131(1988)) has led to the preparation of microporous highly crystalline(particle size>2 μm) molecular sieves that lack appreciable texturalmesoporosity. For the mesoporous molecular sieves of the MCM-41 familythe uniform mesopores are also framework-confined. This has beenverified by TEM lattice images of MCM-41 shown in U.S. Pat. No.5,102,643. Therefore, the framework of this class of materials can beviewed as an expanded version of a hexagonal microporous framework. Theexistence of these framework-confined uniform mesopores was alsoconfirmed by the capillary condensation phenomenon observed in theiradsorption isotherms. The lack of appreciable hysteresis beyondPi/Po>0.4 implies the absence of textural mesoporosity. This lack oftextural mesoporosity is also supported in some cases by the highlyordered hexagonal prismatic shaped aggregates of size>2 μm (Beck et al.,J. Am. Chem. Soc., vol. 114, 10834–10843 (1992)). The total pore volumeof the material reported by Davis et al. is ≈0.7 cm³/g and that of theframework-confined mesopores, as determined from the upper inflectionpoint of that hysteresis loop, is almost equal to that of the total porevolume. Therefore, the ratio of textural to framework-confinedmesoporosity here approaches zero. The size of the framework—confineduniform mesopores is ≈30 Å.

There is a need for mesoporous molecular sieve structures exhibitinghigh thermal and hydrothermal stability (i.e., large frameworkcrosslinking and large wall thickness), small particle size andcomplementary framework-confined and textural mesoporosity. Also, thereis a need for a new preparation art to these ordered mesostructureswhich would allow for cost reduction by employing less expensivereagents and mild reaction conditions while at the same time providingfor the effective recovery and recyclability of the neutral template.

Significant progress has been made recently in extending thesupramolecular assembly of mesostructured inorganic framework structuresto include hierarchical forms with a variety of particle shapes (Ozin,G. A., Acc. Chem. Res. 30 17 (1997); G. A. Ozin, et al., Nature 386 692(1997); Mann, S., et al., Chem. Mater. 9 2300 (1997); Schacht, S., etal., Science 273 768 (1996); and Lin, H. P., et al., Science 273 765(1996)). Mesoporous metal oxide molecular sieves with vesicle-likemorphologies are of special interest as potential catalysts andsorbents, in part, because the mesostructured shells and intrinsictextural pores of the vesicles should efficiently transport guestspecies to framework binding sites. However, all of the vesicle-likemesostructures reported to date have shells of undesirable thickness.More importantly, like many mesoporous molecular sieves withconventional particle morphologies, the framework structures definingthe vesicle shells are lacking in structural stability. For instance, avesicular aluminophosphate with mesoscale d-spacing and surface patternsthat mimic diatom and radiolarian skeletons collapses toAlPO₄-cristobalite with complete loss of the hierarchical patterns at300° C. (Oliver, S., et al., Nature 378 47 (1995)). Also, vesicle-likesilicic acid polymers templated by didodecyldimethylammonium bromidelose their hierarchical structures simply upon washing with alcohols(Dubois, M., et al., Langmuir 9 673 (1993)). Macroscopic hollow spheresof mesoporous MCM-41 (Schacht, Q., et al., Science 273 768 (1996); andHuo, Q., et al., Chem. Mater. 9 14 (1997) have been prepared fromoil-in-water emulsions, but these particles have shells that are verythick (1000–5000 nm) and comparable in size to mesostructures withconventional particle. The feasibility of forming vesicular mesoporoussilicas has been demonstrated recently by an assembly pathway based onthe use of an amine bolaamphiphile as the structure directing agent(Tanev, P. T., et al., Science 271 1267 (1996)). However, the shellthickness (100–250 nm) was large compared to the vesicle diameter(300–800 nm) . More importantly, the thermal and hydrothermal stabilitywas unremarkable, and the particle shape deviated greatly from thedesired vesicular form with increasing surfactant chain length (Tanev,P. T., et al., J. Am. Chem. Soc. 119 8616 (1997)).

Although several surfactant systems are known to direct the assembly oflamellar silica mesostructures (Tanev, P. T., et al., Science 271 1267(1996); Tanev, P. T., et al., J. Am. Chem. Soc. 119 8616 (1997); Kresge,C. T., et al., Nature 359 710 (1992); J. S. Beck et al., J. Am. Chem.Soc. 114 10834 91992); Ogawa, M., J. Am. Chem. Soc. 116 7941 (1994); andLu, Y., et al., Nature 389 364 (1997)), none is capable of generating anentire family of thermally and hydrothermally stable lamellar silicas.Related mesoporous silica art using amine templates to assemblemesostructured silicas is described in U.S. Pat. Nos. 5,672,556,5,712,402, 5,785,946, 5,800,800, 5,840,264 and 5,855,864 to Pinnavaia etal. These products also have relatively poor hydrothermal stability.

SUMMARY OF THE INVENTION

The present invention relates to a lamellar mesoporous silicacomposition containing an electrically neutral gemini amine surfactantin mesopores, the composition having at least one x-ray diffraction peakcorresponding to a basal spacing between about 4 and 10 nm and whereincross-linking of SiO₄ tetrahedra to four adjacent silicon sites (Q⁴) andto three adjacent silicon sites (Q³) corresponds to a Q⁴/Q³ ratio of atleast 5. The notation Q⁴ and Q³ refers to distinguishable linkages forthe SiO₄ units in the silica framework. The silicon atoms in Q⁴tetrahedra are linked through bridging oxygen atoms to four othersilicon centers, whereas the silicon atoms of Q³ tetrahedra are linkedto three other silicon centers through bridging oxygens. Q² and Q¹linkages also are possible, but they occur in very low abundance incomparison to Q³ and Q⁴ linkages. The siting of the SiO₄ tetrahedra inthe framework is readily determined by ²⁹Si NMR spectroscopy. Silicaframeworks with a high Q⁴/Q³ ratio are especially desirable. The largerthe Q⁴/Q³ ratio, the more completely crosslinked and, hence, the morestable, is the framework. All previously reported mesostructured silicasexhibit Q⁴/Q³ ratios near 2.0 in as-synthesized form. Calcining themesostructures increases the ratio to values near 3.0. The especiallylarge Q⁴/Q³ values of at least 5.0 are unprecedented for mesostructuredsilica compositions. Accordingly, these compositions are associated withnovel thermal and hydrothermal stability.

The present invention also relates to a lamellar mesoporous metal oxideand silica composition derived from a silica composition containing anelectrically neutral gemini amine surfactant in mesopores, whichsurfactant has been removed from the silica composition which is thentreated with a compound containing one or more functional inorganicelements and then heating the treated silica composition to form themetal oxide and silica composition.

The present invention further relates to a lamellar mesoporous silicacomposition with at least one x-ray diffraction peak corresponding to abasal spacing of between about 4 and 10 nm and wherein cross-linking ofthe SiO₄ tetrahedra of the silica to four adjacent silicon sites (Q⁴)and to three adjacent silicon sites (Q³) corresponds to a Q⁴ to Q³ ratioof at least 5.

The present invention also relates to a lamellar mesoporous silicacomposition with at least one x-ray diffraction peak corresponding to abasal spacing of between about 4 and 10 nm and wherein cross-linking ofthe SiO₄ tetrahedra sites of the silica to four adjacent silicon sites(Q³) corresponds to a Q⁴ to Q³ ratio of at least 5, and produced from alamellar silica composition containing a neutral gemini amine surfactantwhich is removed to produce the lamellar mesoporous silica composition.

The present invention relates to a method for forming a lamellarmesoporous silica composition which comprises: reacting in a reactionmixture a lower alkyl tetraorthosilicate with a gemini amine surfactantto form the lamellar mesoporous silica composition; and separating thecomposition from the reaction mixture.

Finally, the present invention relates to a lamellar mesoporous silicacomposition containing an electrically neutral gemini amine surfactantin mesopores defining the silica composition.

The present invention discloses that an electrically neutral hydrogenbonding pathway based on the hydrolysis of a silicon alkoxide, such astetraethylorthosilicate (TEOS), in the presence of gemini aminesurfactants at a temperature in a range between about 50 and 150° C.results in the assembly of lamellar silica mesostructures that aremesoporous and exceptionally stable under thermal and hydrothermalconditions. Moreover, the lamellar framework silicas adopt ahierarchical particle structure that is typically vesicular, bowl-like,and ribbon-like in shape. When the assembly is carried out undernon-hydrothermal conditions between about 30 and 50° C., a wormholeframework structure is formed.

The term “particle” as used herein means a fundamental un-agglomeratedobject with a hierarchical shape which is determined microscopically.These fundamental particles agglomerate to form larger aggregates ofparticles. The preferred fundamental particles of the present inventionare in large part vesicular or bowl-shaped with a diameter between about10 and 1400 nm and a shell thickness between about 2.0 and 200 nm whichis quite thin and unique in comparison to the prior art. Preferablythere are between about 1 and 50 nanolayers of silica providing thethickness of the shell. Each silica nanolayer has an elementarythickness in the range 2.0–10 nm. The shell thickness of a vesicle orbowl is determined by the nesting of the nanolayers, one atop another.The nested nanolayers are separated by lower density silica pillars thatcreate channels and pores between the silica lamellae. Vesicular andbowl-shaped particles provide excellent textural mesoporosity andfacilitate access of guest molecules to the adsorption sites and thereaction sites of the lamellar framework structure. Consequently, thecompositions of the present invention are especially useful asadsorbents and heterogeneous catalysts.

The nesting and folding of the framework silica nanolayers affords, inaddition to vesicles and bowl-like particles, fundamental particles withshapes that may be described as folded ribbons, open-ended tubes, andspheres formed by the concentric nesting of spherically folded silicananolayers in a manner akin to the assembly of the structural elementsof an onium. The shapes of these elegant particle objects all resultfrom the folding and nesting of silica nanolayers with a thickness inthe range 3.0–10 nm.

The term “surfactant” means a surface active agent wherein the moleculehas a hydrophobic segment adjacent to a hydrophilic polar head group.The term “gemini amine surfactant” means that the hydrophilic polar headgroup of the surfactant contains at least two (2) amino groups separatedby 1 to 4 carbon atoms. There also can be more than two of the aminogroups contributing to the polarity of the hydrophilic head group. Thegemini amine surfactants that are especially preferred in forming thelamellar mesostructures of the present invention have the followinggeneral molecular structure represented by the formula:RNH(CH₂)_(m)NHR¹wherein R is a hydrophobic segment, R¹ is hydrogen, methyl, ethyl or a—(CH₂)_(m)NH₂ group and m is an integer between 1 and 4. An example of asuitable hydrophobic segment is an aliphatic group of the typeC_(n)H_(2n+1) where n=8 to 20. Gemini amine surfactants of the typeC_(n)H_(2n+1)NH(CH₂)₂NH₂are especially effective in forming the mesostructured compositions ofthe present invention. Linsker, R., et al., J. Am. Chem. Soc. 67 1581(1945) describes the synthesis of some of these gemini aminesurfactants. Some are available commercially.

The pure mesostructured silica compositions of the present invention areuseful as adsorbents and supports for catalysts of different kinds. Forinstance certain acids, such as phosphoric acid and heteropolyacids ofthe type H₃PW₁₂O₄₀, H₄SiW₁₂O₄₀ and polyoxometallate related species, canbe supported in the framework pores of the pure lamellar silicamesostructures. Highly dispersed metals in reduced elemental form, suchas nickel, platinum, palladium, iridium, rhodium, rhenium, ruthenium, aswell as metal oxides, such as SnO₂, V₂O₅, ZrO₂ and many other oxides,and sulfides, such as Co/Mo sulfides, can be supported as nanosizedparticles in the framework pores of the pure silica mesostructures. Allof the said catalytic compounds can be introduced into the frameworkpores of the lamellar mesostructure through the impregnation of suitableprecursors by methods well known to those skilled in the art of catalystformulations.

Although the pure lamellar silica mesostructures of the invention areuseful as high surface area adsorbents and catalyst supports, theybecome even more useful as catalysts and adsorbents when they arefunctionalized through the introduction of one or more reactiveinorganic elements into the lamellar framework structure of themesostructured silica. The introduction of one or more functionalorganic groups into the silica framework, such as those withsequestering properties for metal ions, organic acid-base properties, orany of a large variety of organic functional groups for chemicalcatalysis and for cross-linking the silica framework to a polymermatrix, also greatly extends the utility of the lamellar mesoporoussilicate compositions. Organic functional groups with metal ionsequestering properties, when integrated into the framework of thelamellar silica, behave as metal ion traps for the removal of toxicmetals from contaminated water and waste streams. Organofunctionalgroups with acidic or basic properties allow the functionalized silicasto be used as acidic or alkaline catalysts. Other organicfunctionalities, such as acid anhydride, epoxide, vinyl and many otherwell-recognized reactive moieties, allow the framework to be linkedthrough chemical bond formation to other organic guest molecules in theframework pores and at the external surfaces of the lamellar silicamesostructures. These latter hybrid compositions have many desiredproperties.

A lamellar mesoporous composition wherein the composition has theformula M_(x)Si_(1−x)O_(q) when written in anhydrous form where M is aninorganic element other than silicon or oxygen, x is between about 0.001and 0.35, and y is between about 1.80 and 2.25, the composition havingat least one x-ray diffraction peak corresponding to a basal spacingbetween about 4 and 10 nm and wherein cross-linking of SiO₄ tetrahedrato four adjacent silicon sites (Q⁴) and to three adjacent silicon sites(Q³) corresponds to a Q⁴/Q³ ratio of at least 5.

One or more other inorganic elements can be incorporated into the silicaframework structures of this invention to form lamellar mixed oxides.These functionalized mixed oxide derivatives have compositions ofM_(a)O_(b)—SiO₂ when written in anhydrous form, wherein M is a least oneelement other than silicon or oxygen and a and b provide an elementalbalance in M_(a)O_(b). Alternatively, the compositions of thefunctionalized lamellar mixed oxide derivatives of the present inventionexpressed by the following formula when written in anhydrous form:M_(x)Si_(1−x)O_(q)where M is at least one element which forms an oxide and is preferablyselected from the group consisting of B, Al, Ga, Fe, Co, Mn, Cr, Ge, Ti,V, Ni, Sn, Sb, Zr, W, Mo, Ca, Cu, Pb, In, Nb, Sr, and Zn. In thecalcined composition x is between 0.001 and 0.35 and q is between about1.5 and 2.5. Preferably x is between about 0.005 and 0.35. Preferably qis between about 1.80 and 2.25.

Two general methods may be used to introduce one or more reactiveinorganic elements into the said mixed oxide compositions of thelamellar silica mesostructures of this invention. One method is toincorporate the desired element or elements into the framework as theframework is being assembled in the presence of the gemini aminesurfactant. This is the so-called “direct assembly” pathway to the saidM_(x)Si_(1−x)O_(q) oxide compositions. Alkoxides of the desired elementor elements are preferred as precursors, in part, because they aremiscible with the silicon alkoxides that are used as precursors to thesilica framework. The second, more preferred, method is the so-called“post-synthesis reaction” method wherein the desired element or elementsare introduced into the silica framework through the reaction of thepre-assembled lamellar silica framework structure with a desired elementprecursor. The post-synthesis reaction may be carried out in thepresence of the gemini surfactant in the framework mesopores or, morepreferably, the surfactant can be removed from the silica frameworkmesopores through solvent extraction or calcination prior to reaction ofthe framework with the desired element precursors to afford the desiredM_(x)Si_(1−x)O_(q) compositions.

Ordinarily, the said direct synthesis method provides lamellarM_(x)Si_(1−x)O_(q) compositions wherein the value of x is low, typicallyin the range x=0.001−0.01. At higher values of x, and depending on theelement or collection of elements represented by M, the lamellarframework structure is lost. Alkoxides are the most desired precursorsfor introducing functional M elements into the silica framework by thedirect synthesis route. Alkoxides of many di-, tri-, tetra-, penta- andhexavalent elements are known and many of these are commerciallyavailable. One or more of the precursor alkoxides may be mixed with theprecursor alkoxide of silicon in producing the desiredM_(x)Si_(1−x)O_(q) functional compositions.

The said post-synthesis route to the lamellar M_(x)Si_(1−x)O_(q)compositions of this invention is preferred. Because the lamellarframework is pre-assembled, the lamellar framework, as well as thehierarchical particle morphology, is retained upon insertion of thereactive M centers into the framework. Typically, one or more M speciesmay be inserted into the lamellar silica framework at x values over therange 0.001–0.35. Alkoxides are suitable reagents for the post-synthesispathway to the desired lamellar M_(x)Si_(1−x)O_(q) compositions.However, post-synthesis pathway is not limited to the use of alkoxidesas reagents for the insertion of M centers into the lamellar silicaframework. Many lower-cost salts and metal complexes also are suitablereagents for the post-synthesis pathway to lamellar M_(x)Si_(1−x)O_(q)compositions. For instance, aluminum centers can be introduced into thepreassembled lamellar silica framework by reaction of theas-synthesized, solvent-extracted, or calcined forms of the silicamesostructure with salts of aluminum, such as aluminum nitrate andsodium aluminate. Any aluminum salt is effective in inserting aluminumcenters into the silica framework. M_(x)Si_(1−x)O_(q) compositions withM=Al are especially desired because the aluminum centers introduceacidic sites that are useful in catalyzing important organic chemicalconversions, such as alkylation reactions and cracking reactions.

The present invention provides a route to the synthesis oforganic-inorganic metal oxide compositions with well definedframework-confined mesopores. The compositions produced in the currentinvention are distinguished from those of the prior art by the virtue ofthe method of preparation of the present invention, the subsequentarchitecture of the mesoporous structure and the range of templatedorganic-substituted metal oxides that is afforded by this route.Formation of the mesoporous network is accomplished by interaction(complexation and/or hydrogen-bonding) between a gemini amine surfactanttemplate and neutral inorganic and organic precursors, followed byhydrolysis and subsequent condensation of the inorganic reaction productunder either ambient or elevated temperature reaction conditions and thesubsequent removal of the solvent phase and the template. Thecompositions also have intra- and interparticle textural mesoporosity,in addition to framework mesoporosity.

The present invention particularly provides a preferred nonionic routeto the preparation of quasi-crystalline inorganic-organic oxidecompositions comprising (a) preparing a homogeneous solution or emulsionof a gemini amine surfactant by stirring, sonicating or shaking atambient temperature and pressure; (b) addition of one or more of each ofneutral inorganic and organic precursors with stirring at ambienttemperatures and pressures to the emulsion of step (a) at ambienttemperature to form a precipitated semi-crystalline product; allowingthe mixture to age for a period of time at a temperature between 85° and150° C., more preferably between 100°–120° C.; (c) separating thesolvent and the hydrolyzing agent from the precipitated product byfiltration or centrifugation; and (d) extracting the template throughsolvent extraction whereby the solvent is either water or ethanol, or anethanol-water mixture, or alternatively removing the surfactant throughcalcination at temperatures in excess of 400° C.

The present invention thus provides a new route to mesostructured silicacompositions with uniform, well defined, framework-confined mesoporesthat can be utilized as adsorbents, metal ion traps, solid acids andbases, and catalysts and catalyst supports for the catalytic conversionof organic substrates. According to the method of the present inventionthe formation of the mesoporous structure is accomplished primarily byinteraction (complexation and/or hydrogen bonding) between templatemolecules within micellar aggregates of a gemini amine surfactant andneutral organic and inorganic oxide precursors, followed by hydrolysisand cross-linking of IO_(x) units, wherein between 65 and 100% of the Iunits are SiO₄ units and the remainder are metallic or non-metallicelements coordinated to x oxygen atoms (2≦x≦8). This interaction is mostlikely to occur between an I—OH unit and the NH₂ functions of eachsurfactant molecule, or between the I—OH unit and the array of lone pairelectrons on the template polar segment. The polar segment of thetemplate in the present invention is flexible and appears to act in thefashion of a ligand complexing through hydrogen bonding to a I—OH unit,thereby stabilizing a site of nucleation for subsequent condensation ofthe mesoporous quasi-crystalline organic and inorganic oxide product,although the inventors do not want to be bound to any particular theory.

The prior art does not describe the preparation of micro-, meso-, ormacro-porous inorganic oxide compositions by such a nonionic mechanisminvolving crystallization of organic and inorganic oxide precursorsaround well defined micelles of the gemini amine surfactants.Specifically, the present results are achieved by using micelles of thesurfactant to template and assemble neutral inorganic and organicreactant precursors into a mesoporous framework structure. Complexationand/or hydrogen bonding between the template and the reagent is believedto be the primary driving force of the assembly of the framework in thecurrent invention. The aforementioned method consists of the formationof a solid precipitate by the mixing of a solution or emulsion ofelectrically neutral gemini amine surfactant, with a neutral inorganic,usually inorganic alkoxide, and an organic oxide precursor in thepresence of a hydrolyzing agent, followed by aging assembly temperaturesbetween ambient and 150° C. for at least 8 hours. The template may berecovered by extraction with ambient temperature alcohol or hotwater-ethanol mixtures or it can be removed by calcination attemperatures above 500° C. Thus both the compositions and methodologiesof the present invention differ fundamentally from previous art in whichcationic gemini surfactants are used to assemble mesostructures (Huo, etal., Science, 268 1324 (1995)). When the gemini surfactant is madecationic through the presence of quaternary ammonium ions on the polarhead group, as disclosed in the prior art of Huo et al, the assemblyreaction is under electrostatic (columbic) control and differentmesostructured frameworks are formed.

The template may be removed from the condensed reaction products bysolvent extraction of the template from the air dried material using anorganic solvent such as an alcohol or using hot water or using a hotalcohol-water mixture.

The synthesis methods for the formation of MSU-G materials involve thepreparation of solutions or emulsions of a gemini amine surfactanttemplate compound and reaction of this solution with a silicon alkoxideprecursor and optionally including di-, tri-, tetra-, penta- orhexa-valent metal or metalloid hydrolyzable alkoxide reagents andoptionally including an organic silane in the presence of a hydrolyzingagent under static, stirring, sonication or shaking and conditions attemperatures in the range 85–150° C. until formation of the desiredprecipitated product is achieved and recovering the solid material.

The inorganic oxide precursors are single or double metal alkoxidecompounds, The list of preferred alkoxides includes but not exclusively:aluminum(III) ethoxide, aluminum(III) isopropoxide, aluminum(III) n-,sec- or tert-butoxide, antimony(III) isopropoxide, antimony (III)n-butoxide, calcium(II) ethoxide, calcium(II) isopropoxide, calcium(II)tert-butoxide, chromium(IV) isopropoxide, chromium(IV) tert-butoxide,copper(II) methoxyethoxide, gallium(III) isopropoxide, germanium(IV)ethoxide, germanium(IV) isopropoxide, indium(III) isopropoxide,iron(III) ethoxide, iron(III) isopropoxide, iron(III) tert-butoxide,lead(II) isopropoxide, lead(II) tert-butoxide, magnesium(II) ethoxide,manganese (II) isopropoxide, molybdenum(v) isopropoxide, niobium(V)ethoxide, silicon(IV) methoxide, silicon(IV) ethoxide, silicon(IV)propoxide, silicon(IV) butoxide, silicon(IV) hexoxide, strontium(II)ethoxide, tin(IV) isopropoxide, titanium(IV) ethoxide, titanium(IV)propoxide, titanium(IV) isopropoxide, titanium(IV) butoxide,titanium(IV) octadecoxide, tungsten(VI) ethoxide, tungsten (VI)isopropoxide, vanadium(V) triisopropoxide oxide, zinc(II) isopropoxide,zinc(II) tert-butoxide, zirconium(IV) n-propoxide, zirconium(IV)isopropoxide, zirconium(IV) butoxide, zirconium(IV) tert-butoxide,aluminum(III)silicon(IV) alkoxide, titanium(IV)silicon(IV) polyethoxideand other mixtures of the aforementioned alkoxide compounds. Thealcohols used in step (i) of the preparation art correspond to thealcoholate ligand from which the metal alkoxide is derived. The alcoholsthus preferred are methanol, ethanol, n- and isopropanol and n-, sec-,tert-, butanol. The alcohols contain 1 to 4 carbon atoms.

A lamellar mesoporous composition wherein the composition has theformulas selected from the group consisting of [(R₁)SiO_(3/2)]_(x)SiO₂,[(R₁)₂SiO]_(x)SiO₂, and [(R₁)₃SiO_(1/2)]_(x)SiO₂ and mixtures thereof,when written in anhydrous form where R₁ is an organic moiety containingan organic functional group and x is between about 0.01 and 0.30, thecompositions having at least one x-ray diffraction peak corresponding toa basal spacing between about 4 and 10 nm and wherein cross-linking ofSiO₄ tetrahedra to four adjacent silicon sites (Q⁴) and to threeadjacent silicon sites (Q³) corresponds to a Q⁴/Q³ ratio of at least 5.

The silica composition of this invention also can contain a substitutedorgano silane as discussed, for example, by Richer et al., Chem. Commun.1775–1776 (1998) and Brown et al., Chem. Commun. 69–70 (1999). Thematerials provide unique surface properties in the as-formed silicacomposition. These compositions can be produced by direct incorporationof an organosilane during the assembly of the lamellar silica frameworkor the organo groups can be introduced by post-synthesis reaction of thesurface hydroxyl groups of the framework with a suitable organosilane.The post-synthesis method is preferred.

These organo functional derivatives of the lamellar mesostructures ofthe present invention have the following compositions when written inanhydrous form: [(R₁)SiO_(3/2)]_(x)SiO₂, [(R₁)₂SiO]_(x)SiO₂ and[(R₁)₃SiO_(1/2)]_(x)SiO₂ where R₁ is an organic moiety, preferablycontaining an organo functional group and X is between about 0.01 and0.30. These compositions have about the same range of XRD basal spacingsand XRD and Q⁴/Q³ ratios as have been described above for the puresilica frameworks.

The organic silanes which are useful in producing the saidorgano-functional lamellar silica compositions of the present inventionare those which will react to form the mesoporous structure in adirect-synthesis pathway and those that will react with thepre-assembled lamellar silica in a post-synthesis reaction pathway.Included are preferred silanes of the formula:(RO)₃SiR₁, (RO)₂Si(R₁)₂ and ROSi(R₁)₃,where R is hydrogen or a lower alkyl group (1 to 8 carbon atoms). Thegeneral formula is Si(OR)_(4−n)(R₁)_(n) where n is 1, 2 or 3. Anotherway of expressing the useful silane reagents for the introduction oforganic functionality into the lamellar silica framework is through thegeneral formulas X₃Si(R₁), X₂Si(R₁)₂ and XSi(R₁)₃ where X is anyhydrolyzable group which reacts with silica. R₁ in the above formulascan be the same as R and can be an organic group which is non-reactivewhich can be an alkyl, alkoxy, alkenyl or alkynyl, cycloaliphatic,aromatic group containing 1 to 25 carbon atoms. R₁ can includesubstituents of O, N or S and can provide a hydroxide, an aldehyde,acid, base, sulfide, cyanide, mercaptan and the like. Examples of basicmoieties especially useful as catalysts include amines and pyridylgroups. Useful acidic functionalities include carboxylic acids, sulfonicacids, and fluorinated sulfonic acids. R₁ can contain a halogen selectedfrom the group consisting of F, I, Br or Cl and the R₁ group can befurther reacted at the halogen group. The preferred R₁ contain moietieswhich are metal binding to provide selective adsorption of metal ionsfrom solution. Especially useful metal trapping agents include organicgroups containing chelating ligands such as ethylene diamines, ethylenediamine tri- and tetra acetate, cyclic and bicyclic polyethers known ascrown ethers and cryptans and the like. The mixed metal alkoxides andorganic-alkoxy silanes can be obtained commercially. Alternatively, theymay be specifically prepared for use in forming the desiredcompositions. Functional organosilanes can be prepared byhydrosilylation of olefins. The desired organo-functional lamellarsilica compositions may be prepared most preferably by reaction of theparent lamellar silica with a said organosilane under reflux in toluenefor 3–4 hours.

Preferably the R₁ group of the said Si(OR)_(4−n)(R₁)_(n) silanescontains a functional group selected from a metal complex, vinyl, cyano,amino, mercapto, halogen (usually Cl or Br), aldehyde, ketone acid(including sulfonic and F-sulfonic acid or base group). The metalcomplex functionality helps form structures where the metal is removableand provides increased receptivity to the metal removed.

Examples of commercially available functional silanes which can be usedare:

-   3-(N-allylamino)propyltrimethoxy-silane;-   O-allyloxy(polyethyleneoxy)-trimethylsilane;-   N-(2-aminoethyl)-3-aminopropylmethyl-dimethoxysilane;-   N-(2-aminoethyl)-3-aminopropyltri-methoxysilane    N-[3-(trimethoxysilyl)propyl]ethylenediamine;-   N-(6-aminohexyl)aminopropyl-trimethoxysilane;-   2-[Methoxy(polyethyleneoxy)propyl]trimethoxysilane;-   (3-Trimethoxysilylpropyl)diethylene-triamine 95%;-   Trivinylmethoxysilane;-   3-Cyanopropyldimethylmethoxysilane;-   3-Cyanopropyltriethoxysilane;-   (3-Cyclopentadienylpropyl)triethoxysilane;-   Diphenyldiethoxysilane;-   Diphenyldimethoxysilane;-   Diphenylsilanediol;-   Diphenylvinylethoxysilane;-   (Mercaptomethyl)dimethylethoxysilane;-   (Mercaptomethyl)methyldiethoxysilane;-   3-Mercaptopropylmethyldimethoxysilane;-   3-Mercaptopropyltrimethoxysilane;-   3-Mercaptopropyltriethoxysilane;-   3-Methacryloxypropyldimethylethoxy-silane;-   3-Methacryloxypropyldimethylmethoxysilane;-   3-Methacryloxypropylmethyldiethoxy-silane;-   3-Methacryloxypropylmethyldimethoxysilane;-   3-Methacryloxypropyltrimethoxysilane;-   Methylphenyldimethoxysilane;-   Methyl[2-(3-trimethoxysilylpropylamino)-ethylamino]-3-propionate    (65% in methanol);-   7-Oct-1-enyltrimethoxysilane;-   Phenethyltrimethoxysilane;-   N-Phenylaminopropyltrimethoxysilane;-   Phenyldimethylethoxysilane;-   Phenyltriethoxysilane;-   Phenyltrimethoxysilane;-   Phenylvinyldiethoxysilane;-   N-[3-(triethoxysilyl)propyl]-4,5-dihydro-imidazole;-   2-(Trimethoxysilyl)ethyl-2-Pyridine;-   Trimethoxysilylpropyldiethylenetriamine (95%);-   N[(3-trimethoxysilyl)propyl]ethylene-diamine triacetic acid,    trisodium salt (50% in water);-   N-(3-trimethoxysilylpropyl)pyrrole;-   Triphenylsilanol;-   Vinyldimethylethoxysilane;-   Vinylmethyldiethoxysilane;-   Vinyltriethoxysilane;-   Vinyltrimethoxysilane;-   N-(trimethoxysilylpropyl)ethylene-diamine, triacetic acid, trisodium    salt;-   4-Aminobutyldimethylmethoxysilane;-   4-Aminobutyltriethoxysilane (95%);-   N-(2-aminoethyl)-3-aminopropylmethyldi-methoxysilane;-   H₂NCH₂CH₂CH₂SiOEt 3-aminopropyldimethylethoxysilane;-   3-Aminopropylmethyldiethoxysilane;-   3-Aminopropyldiisopropylethoxysilane;-   3-Aminopropyltriethoxysilane;-   3-Aminopropyltrimethoxysilane;-   N-(triethoxysilylpropyl)urea (50% in methanol)-   N-[3-(triethoxysilyl)propyl]phthalamic acid (95%).

The above list is not meant to be limiting, but merely intended toprovide examples of easily obtainable functional silanes useful inpreparing the compositions of this invention. In general, any functionalorganosilane may be incorporated into the porous inorganic and organicoxide materials embraced by the present art. Functional organo groups onthe silane moiety that are especially useful include acids and bases forcatalytic applications, dye chromophores for sensing, linking groups(e.g. epoxides, acid anhydrides, amines, esters, carboxylates and thelike) for forming polymer-inorganic nanocomposites, and complexants forbinding metal ions. In the latter case the bound metal ions may berecovered by ion exchange or subsequently used in the immobilized stateas catalysts for organic chemical transformation.

The templated mesostructured silica compositions of the presentinvention can be combined with other components, for example, zeolites,clays, inorganic oxides or organic polymers or mixtures thereof. In thisway adsorbents, ion-exchangers, catalysts, catalyst supports orcomposite materials with a wide variety of properties may be prepared.Additionally, one skilled in the art may impregnate or encapsulatetransition metal macrocyclic molecules such as porphyrins orphthalocyanins containing a wide variety of catalytically active metalcenters.

Additionally, the surfaces of the compositions can be functionalized inorder to produce catalytic, hydrophilic or hydrophobic surfaces. Thesurfaces may be functionalized after synthesis by reaction with variouschlorides, fluorides, silylating or alkylating reagents.

In the present invention the gemini amine surfactants can be removedfrom the as-synthesized mesostructures by solvent extraction to formsurfactant-free mesostructures. Useful solvents include polar moleculessuch as water, alcohols, ketones, nitrides and the like. Preferred isethanol. The surfactant can also be removed from the as-synthesizedmesostructure by calcination. However, preferably the surfactant isremoved prior to calcination and can be recycled.

Calcination of the as-synthesized and solvent-extracted mesostructuresis achieved at temperatures between about 200° and 1000° C. Furnaces foraccomplishing calcination are well known to those skilled in the art.

OBJECTS

It is therefore an object of the present invention to provide novelmesoporous lamellar silica compositions which preferably contain one ormore functional inorganic elements or functional organic moieties aspart of the lamellar framework structure. Further objects are to providelamellar silica compositions with high thermal and hydrothermalstability and a unique particle structure. Further still it is an objectof the present invention to provide a process for the preparation of thenovel silica compositions. Further, it is an object of the presentinvention to provide silica compositions which are relatively simple toprepare and are economical because of recycling of the unique neutraltemplate used for forming the silica compositions. These and otherobjects will become increasingly apparent by reference to the followingdescription and the drawings.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1A is a schematic illustration of the pathway used for thepreparation of mesostructured MSU-G silicas. FIGS. 1B and 1C are XRDpatterns shown in FIG. 1C for the pristine surfactant which wererecorded for a 88:12 (v/v) water:ethanol suspension of neutral C °₁₂₋₂₋₀gemini amine surfactant (C₁₂H₂₅NH(CH₂)₂NH₂) at the same concentration(3.0 wt %) used for MSU-G synthesis and a thin film sample of thesurfactant on glass. The XRD pattern for the as-made and calcined MSU-Gsamples are shown in the FIG. 1C. The patterns were obtained on a RigakuRotaflex Diffractometer equipped with a rotating anode and Cu K_(α)radiation (λ=0.1542 nm).

FIGS. 2A and 2B are TEM images of calcined (650° C.) hierarchical formsof lamellar silica assembled from a C₁₂H₂₅NH(CH₂)₂NH₂ gemini aminesurfactant. FIG. 2A shows the dominant vesicular morphology. The arrowpoints to one of the largest vesicles with a diameter of ˜1400 nm and ashell thickness of approximately 40 nm. FIG. 2B contains fracturedmultilamellar vesicles and bowls. Framework mesopores are containedbetween the undulated silica sheets of the multilamellar vesicles. Eachsilica layer is ˜3 nm thick. FIGS. 2B and 2D also show the presence ofwormhole-like framework pores that run orthogonal to the undulatedsilica sheets, making the pore network three dimensional. The arrows inFIG. 2C point to unilamellar vesicles ˜20 nm in diameter. The samehierarchical forms were observed for silicas assembled from geminisurfactants containing alkyl chains with 10 and 14 carbon atoms. Themicrographs were obtained on a JEOL 100CX instrument with an electronbeam generated by a CeB₆ gun operating at an acceleration voltage of 120kV. The specimens were loaded onto a holy carbon film supported on acopper grid by dipping the grid into a suspension of the silica (1 wt %)in ethanol.

FIG. 3A is a graph showing N₂ adsorption/desorption isotherms forcalcined (650° C.) lamellar silicas assembled fromC_(n)H_(2n+1)NH(CH₂)₂NH₂ surfactants (n=10, 12 and 14). FIG. 3B providesthe Horvath-Kawazoe pore size distributions obtained from the adsorptionbranch of the isotherms. The isotherms were obtained on a MicromeriticsASAP 2010 Sorptometer at −196° C. Samples were out-gassed at 150° C.overnight under vacuum (10⁻⁵ torr) . Isotherms B and C have been offsetby 100 and 300 cc/g, respectively, along the vertical axis for clarity.

FIG. 4 is a graph showing: (A) the experimental ²⁹Si-MAS-NMR spectrum ofas-synthesized lamellar silica mesostructure assembled using the geminisurfactant C₁₂H₂₅NH(CH₂)₂NH₂ as the structure director. Curve (B) is thesum of the deconvoluted Q⁴ and Q³ spectral components represented bycurves (C) and (D), respectively, with relative integral intensities of6.2:1.0. The single pulse mode ²⁹Si MAS NMR spectrum was recorded on aVarian 400 VRX spectrometer using a 7 mm zirconia rotor, a spinningfrequency of 4 kHz, and a pulse delay of 800 s.

FIG. 5 is a graph showing a X-ray powder diffraction pattern of theproduct of calcined Example 2 at 650° C. for 4 hours.

FIG. 6 displays the N₂ adsorption and desorption isotherms for theproduct of MCM-41. Curve (A) for calcination at 650° C. for 4 hours.Curve (B) for calcination at 1000° C. for 4 hours. Curve (C) for thecalcined sample (650° C.) after hydrothermal treatment in H₂O at 100° C.for 56 hours.

FIG. 7 displays the N₂ adsorption and desorption isotherms for theproduct of KIT-1. Curve (A) is for the sample calcined at 650° C. for 4hours. Curve (B) is for the calcined sample at 1000° C. for 4 hours.Curve (C) is for the calcined sample (650° C.) after hydrothermaltreatment in H₂ at 100° C. for 56 hours.

FIG. 8 displays the N₂ adsorption and desorption isotherms for thelamellar mesostructured silica product of Example 2. Curve (A) is forthe sample calcined at 650° C. for 4 hours. Curve (B) is for the samplecalcined at 1000° C. for 4 hours. Curve (C) is for the calcined sample(650° C.) after hydrothermal treatment in H₂O at 100° C. for 56 hours.

FIG. 9 is a X-ray powder diffraction pattern of the lamellarmesostructured silica product of Example 2 after calcination at 1000° C.for 4 hours.

FIG. 10 is a ²⁷Al MAS NMR spectrum of the lamellar mesostructured silicaproduct of Example 2 as-synthesized (A) and calcined at (B) of Example2.

FIG. 11 is a graph showing XRD patterns for the product formed accordingto Example 13; (A) as synthesized and (B) after calcination at 650° C.

FIG. 12 is a TEM image of the calcined (650° C.) sample preparedaccording to Example 19.

DESCRIPTION OF PREFERRED EMBODIMENTS

The new family of mesoporous molecular sieves (denoted herein as MSU-G)with vesicle-like hierarchical structures and unprecedented thermal andhydrothermal stabilities were preferably prepared through asupramolecular assembly pathway that relies on hydrogen bonding betweenelectrically neutral gemini amine surfactants most preferably of thetype C_(n)H_(2n+1)NH(CH₂)₂NH₂ and silica precursors derived from siliconalkoxides, most preferably tetraethylorthosilicate. The mesostructuredframework is constructed of one or more undulated silica sheets ˜3 nmthick with mesopores running parallel, as well as orthogonal to thesilica sheets, making the framework structure bicontinuous and highlyaccessible. The silica framework lamellae fold into vesicle- andbowl-like particles, as well as other particle shapes, that introducetextural mesoporosity and facilitate access to the framework surfaces.Depending on the choice of surfactant chain length and the use ofco-surfactants, framework mesopores with average diameters of 2.0–10.0nm are obtainable. Functional elements (e.g., Ti(IV) and Al(III)) havebeen incorporated into the framework with retention of hierarchicalstructure. The exceptional structural stability of the mesostructuredframework under thermal (1000° C.) and hydrothermal conditions (100°C., >150 h) is associated with intrinsically high Q⁴/Q³ SiO₄crosslinking values of at least 5.0. These new mesostructures areespecially promising materials for applications in heterogeneouscatalysts and molecular separations.

The present invention provides a direct and highly efficient synthesisroute to a novel family of lamellar mesoporous silicas andfunctionalized derivatives of these silicas containing other inorganicelements and organo groups as part of the lamellar framework (denotedMSU-G). Vesicular and bowl-shaped particles with very thin shells (˜2 to70 nm) and diameters of 20 to 1400 nm are often formed through thenesting and folding of the framework lamellae. The vesicle andbowl-shaped particles may be comprised of single framework lamellae 3–10nm thick or they may be formed through the nesting of many (up to 50)lamellae from the said particles with multi lamellae shells. Moreover,the degree of framework SiO₄ unit crosslinking is unprecedented amongmesoporous silicas, making these materials ultrastable relative topreviously reported mesostructures.

As illustrated schematically in FIG. 1B, MSU-G silicas were obtained bythe cooperative transformation of a silicon alkoxide (TEOS) and alamellar C °_(n-2-0) surfactant phase into an undulated lamellarmesostructure under hydrothermal reaction conditions. For instance, aMSU-G mesostructure was prepared by the hydrolysis and polymerization ofTEOS in a 1:9 (v/v) ethanol: water solution of a neutral C °_(n-2-0)gemini surfactant under hydrothermal conditions. The molar ratio of eachreaction mixture was 1.0 TEOS:0.25 surfactant:4.3 EtOH:78 H₂O. TEOS wasadded to the surfactant in the water:ethanol mixed solvent under rapidstirring for 3 minutes, and then the mixture was heated at 100° C. in anautoclave for 48 hours under static conditions. The product wasfiltered, washed with cold ethanol and dried in air. Finally, thesurfactant was removed from the as-made product by calcination in air at650° C. for 4 hours or by extraction with hot ethanol. The XRD patternof the initial surfactant solution in the absence of TEOS revealed thepresence of two lamellar phases with basal spacings (3.56 and 3.29 nm)that differ by one water layer between lipid-like bilayers. These twophases also are observed for a thin film sample of the surfactantsupported on glass. The as-synthesized MSU-G mesostructures and thesurfactant-free forms obtained by calcination at 650 and 100° C. exhibitone (001) diffraction line or, at most, two diffraction lines (001, 002)consistent with an undulated lamellar structure.

The representative TEM image shown in FIG. 2A illustrates the lamellarframework structure and vesicular particle morphology of MSU-G silicas.Three C °_(n-2-0) surfactants with n=10, 12 and 14 all form silicamesostructures with the same dominant vesicle-like shapes. Nearly all ofthe particles (>90%) may be described as being complete vesicles or,more commonly, ruptured vesicles (FIGS. 2B, 2C), and bowls (FIG. 2D).The rims of the bowls and the edges of the ruptured vesicles clearlyreveal a framework structure made up of undulated silica layersapproximately 3.0 nm thick with irregularly spaced mesopores runningparallel to the lamellae. Bridging of the silica layers is also evidentin the micrographs. In addition, the rounded surfaces of the vesicularand bowl-shaped fragments show randomly distributed framework poresorthogonal to the silica sheets. Consequently, each 3-nm thick sheetcontains mesopores that connect to the interlayer mesopores, allowingthe pore system to be three-dimensional. Consisting with vesicleformation through a layer propagation and bending process, the smallervesicles with diameters in the range ˜20–125 nm have very thinunilamellar shells (˜3 nm), whereas the larger vesicles with diametersup to 1400 nm have multilamellar shells up to ˜70 nm in thickness.

FIG. 3 shows the N₂ adsorption-desorption isotherms and Horvath-Kawazoe(HK) pore size distributions for calcined MSU-G silicas prepared fromgemini surfactants of differing alkyl chain length. The adsorption stepsat relative pressures between 0.20 and 0.65 signify the filling offramework mesopores, and the hysteresis loops at higher relativepressures are a consequence of N₂ filling the textural mesoporesassociated with a vesicular (lamellar) particle morphology. In accordwith an assembly pathway based on hydrogen-bond interactions between thesurfactant and the inorganic framework walls, the surfactant could bereadily removed from the framework pores by hot ethanol extraction, asjudged by ¹³C CP MAS NMR. The N₂ adsorption and desorption isotherms forthe solvent extracted samples were nearly identical to those obtainedfor the calcined derivative.

As summarized in Table 1 hereinafter, the maxima in the HK pore sizedistribution curves increase in the order 2.7, 3.2 and 4.0 nm as thesurfactant chain length is increased over the range n=10, 12, 14,respectively. Also, an increase in the surfactant chain length increasesboth the d-spacing and the pore size. Consequently, the framework wallthickness (FWT) remains almost constant (2.1–2.5 nm) and in reasonableagreement with the value estimated from TEM images (˜3.0 nm).Interestingly, the FWT values are about 2.5 to 3.0 times larger than thevalues observed for electrostatically assembled MCM-41 silicas(Alfredsson, V., et al., J. Chem. Soc. Chem. Common. 921 (1994); andTanev, P. T., et al., Chem. Mater. 8 2068 (1996)). Accordingly, thethicker framework walls result in BET surface areas (280–520 m²/g) thatare proportionately lower than the values typically found for MCM-41(900–1200m²/g)

A further important distinction between MSU-G silicas and previouslyreported mesoporous silicas is the very high degree of SiO₄ unitcrosslinking in the framework and the structural stability that resultsfrom this crosslinking. As shown by the deconvoluted ²⁹Si MAS NMRspectra in FIG. 4, the as-made MSU-G framework consists primarily offully crosslinked Q⁴ SiO₄ units with a resonance near −100 ppm, and asmaller fraction of incompletely crosslinked Q³ sites (−98 ppm). Threedifferent as-made MSU-G mesostructures yielded Q⁴/Q³ ratios in the range6.2 to 7.4 (c.f., Table 1). Normally, as-made silica mesostructures,whether assembled from ionic or neutral surfactants, exhibit Q⁴/Q³ratios ≦2.0, and their calcined derivatives typically have values near3.0 (Kresge, C. T., et al., Nature 359 710 (1992); J. S. Beck, et al.,J. Am. Chem. Soc. 114 10834 (1992); and Alfredsson, V., et al., J. Chem.Soc. Chem. Common. 921 (1994)). Interestingly, the Q⁴/Q³ ratios forMSU-G do not change greatly upon calcination at 650° C., suggesting thatthe SiOH groups may be site isolated and buried in the framework.

Consistent with the remarkable degree of framework crosslinking, thethermal and hydrothermal stabilities of MSU-G silicas are unprecedentedamong all previously reported mesostructures, regardless of frameworkcomposition or framework structure. In addition to being structurallystable to calcination at 1000° C. (c.f., FIG. 1B), MSU-G silicas arestable in boiling water for >150 hr. In contrast, it was found thatMCM-41 and other electrostatically assembled silicas with benchmarkedhydrothermal stabilities, including framework-stabilized KIT-1 silicamesostructures (Ryoo, R., et al., Stud. surf. Sci. Catal. 105 45 (1997);Ryoo, R., et al., J. Phys. Chem. 100 17718 (1996)) and the thick-walledSBA-15 family of silicas (Zhao, D., et al., Science 279 548 (1998)),become X-ray amorphous and lose accessible framework mesoporosity inless than 50 hours when subjected to equivalent hydrothermal conditions.The lamellar silica phases assembled in the presence of bolaamphiphileamines (Tanev, et al., J. Amer. Chem. Soc., 119 9164 (1997)) alsodecompose in less than 50 hours in water at 100° C.

The combination of a three-dimensional pore network and a vesicle-likehierarchical morphology for MSU-G silicas, in addition to theirremarkable thermal and hydrothermal stability, has importantimplications for their use in chemical catalysis and molecularseparations. Most mesostructured molecular sieves, particularly thoseprepared through an electrostatic pathway, exhibit framework porelengths on a micrometer length scale, comparable to the length scale ofthe mesostructured particles themselves. Consequently, access to theframework sites can be limited by diffusion along the pore length,particularly for reactions in condensed media. A combined vesicularmorphology and three-dimensional pore network allows the averagediameter and length of the mesopores within a particle to be morecomparable in their dimensions, thus greatly facilitating access. As afirst step toward the catalytic applications of such structures,redox-active Ti(IV) and acidic Al(III) centers have been incorporatedinto the framework of MSU-G silicas through post-synthesis reactionswith titanium isopropoxide and sodium aluminate without altering thelamellar framework or the vesicular hierarchical structure.

EXPERIMENTAL EXAMPLES 1 TO 3

Thirty five milliliters of deionized H₂O was mixed with five millilitersof ethanol under stirring and the appropriate amount of neutral Geminisurfactant template (see Table 1) was added. These neutral Geminisurfactants used in the preparation were synthesized by previouslydescribed procedures (F. Linsker and R. L. Evans, J. Am. Chem. Soc., 67,158 (1945)). The resultant mixture was stirred at room temperature for20 hours until a milky solution of template was obtained. A 5.2gram-quantity of Si(OC₂H₅)₄ was added to the above solution of templateand stirred at room temperature for 3 minutes. The reactionstoichiometry expressed in terms of moles per mole SiO₂ corresponded tothe following:

0.25 moles C_(n)H_(2n+1)NH(CH₂)₂NH₂

78 moles H₂O

4.3 moles of EtOH.

The resulting gels were transferred into a Teflon-lined autoclave andaged at 100° C. for 48 hours under autogenous pressure. After theautoclave was cooled to room temperature, the as-synthesized productswere filtered, washed with water and ethanol, and air-dried. Thetemplate was removed through solvent extraction and(or) calcination inair at 650° C. for 4 hours.

The X-ray diffraction patterns of all samples were measured on a RigakuRotaflex diffractometer equipped with rotating anode and Cu—K_(α)radiation (λ=0.15148 nm). The diffraction data were recorded bystep-scanning at 0.02 degrees of 2θ per step, where θ is the Braggangle. The d-spacing of the X-ray reflections of the samples werecalculated in Angstrom units (Å). Transmission electron micrographs wereobtained on a JEOL JEM 100CX II electron microscope. The specimen wassuspended in ethanol loaded on carbon coated copper grids (400 mesh).The sample images were obtained using an accelerating voltage of 120 kV,a beam diameter of approximately 5 μm and an objective lens aperture of20 μm. The single-pulse mode ²⁹Si MAS NMR spectrum was recorded on aVarian VXR-400S spectrometer with a 7 mm zirconia rotor, a spinningfrequency of 4 kHz and a pulse delay of 800 s. The pore structure of thesaid samples was characterized by measuring the N₂ adsorption-desorptionisotherms on a Coulter Omnisorp 360 CX Sorptometer at −195° C. usingstandard continuous sorption procedures. Before the measurement, eachsample was heated overnight at 150° C. and 10⁻⁶ Torr. The specificsurface area (S_(BET), m²/g) and the total pore volume (V_(t), cc/g)were calculated from the isotherms following the IUPAC recommendations(Sing et al., Pure Appl. Chem. 57, 603–619 (1985)) . The pore sizedistribution of the materials was calculated using the method of Horvathand Kawazoe (G. Horvath and K. J. Kawazoe, J. Chem. Eng. Jpn., 16,470–475 (1983)). Thermogravimetric analyses of the samples wereperformed under a flow of dry N₂ gas on a CAHN system thermogravimetricgas (TG) analyzer using a heating rate of 5° C./min. The amounts of eachsurfactant used in the Examples 1–3, together with the correspondingphysicochemical parameters are summarized in Table 1.

TABLE 1 Amount HK BET Template of pore Surface Wall chain Template d₀₀₁size area^(a) thickness^(b) Example length used (g) (Å) (Å) (m²/g) (Å)Q⁴/Q^(3c) 1 C₁₀ 1.25 48.0 27 523 21 7.1 2 C₁₂ 1.43 56.6 32 412 25 6.2 3C₁₄ 1.60 64.9 40 279 25 7.4 ^(a)The framework-confined mesoporous sizewas determined by Hovarth-Kawazoe (HK) analysis of the N₂ adsorptionisotherm. ^(b)The framework wall thickness is determined by subtractingthe HK mesopore size from the d-spacing. ^(c)Q⁴/Q³ ratios for theframework SiO₄ units in as-synthesized products.

The X-ray diffraction pattern of the calcined product of Example 2 isshown in FIG. 5. It exhibits a sharp and strong relative intensity peakat 56±1.0 Å d-spacing. The transmission electron microscope (TEM) imageof this product, presented as FIGS. 2A to 2C shows typical vesicularmorphology with undulated silica layers. The N₂ adsorption-desorptionisotherms and Horvath-Kawazoe (HK) pore size distributions for calcinedproducts are shown in FIGS. 3A and 3B. The adsorption steps at relativepressures between 0.20 and 0.65 signify the filling of frameworkmesopores, and hysteresis loops at higher relative pressures are aconsequence of N₂ filling the textural mesopores that are associatedwith a vesicular (lamellar) particle morphology. The data in Table 1reveal that the compositions of the present invention possess muchlarger framework wall thickness (from 21 to 25 Å) than the reported ofMCM-41 (from 8 to 12 Å). Thus, our compositions are expected to possessa much higher thermal and hydrothermal stability than that observed forthe other mesoporous materials. The as-synthesized products yielded highQ⁴/Q³ ratio (cross-linked SiO₄) in the range from 6.2 to 7.4. Thisremarkable high Q⁴/Q³ ratios for as-synthesized products (FIG. 4) areover 3 times higher than those of MCM-41 and HMS silicas (less than2.0). To distinguish this new family Mesoporous silica molecular sievesfrom others, they are designated as MSU-G molecular sieves.

COMPARATIVE EXAMPLES 4–5

The following examples were prepared to test the thermal andhydrothermal stabilities of MCM-41 and KIT-1 samples which can be- thecomparison for the stability of the product of Example 2. The thermaland hydrothermal stability of mesoporous materials is a crucial factorfor practical applications.

MCM-41 used in the Example 4 was prepared at 100° C. for 4 d by reportedprocedure involving a sequential acid titration approach using H₂SO₄(White et al., Chem. Mater., 9, 1226 (1997)). KIT-1 used in the Example5 was made using cetyltrimethylammonium chloride and sodium silicate(LUDOX-40) under basic conditions in the presence of large amounts ofNa₄EDTA as a structure promoter (Ryoo et al., Stud. Surf. Sci. Cat.,105, 45 (1997)). The reason for choosing KIT-1 was that KIT-1 wasclaimed to be a better material for thermal and hydrothermal stabilitythan conventionally prepared MCM-41.

The thermal stability of samples was tested at 1000° C. for 4 hours inthe air. The hydrothermal stability of the product was investigated bymixing 0.1 grams of the calcined product at 650° C. for 4 hours with 10milliliters deionized water and heating in a closed bottle at 100° C.under static conditions. The stability was examined by XRD and N₂adsorption-desorption isotherms.

FIG. 6 shows the N₂ adsorption-desorption isotherms of MCM-41 aftercalcinations at 1000° C. for 4 hours and hydrothermal treatment in H₂Oat 100° C. for 56 hours, respectively. After these treatments MCM-41shows no steps in the N₂ adsorption isotherm corresponding to frameworkmesopores filling between P/P_(o)at 0.2 and 0.4. This result indicatesthat MCM-41 suffered structural degradation to amorphous silica afterthe treatments. After calcination at 1000° C. for 4 hours, KIT-1 stillshows a N₂ filling step for mesopores between P/P_(o) at 0.2 and 0.3(FIG. 7), but the pore volume of the sample (0.35 cm³/g) decreased by75% relative to that of the calcined sample at 650° C. for 4 hours (0.79cm³/g). The KIT-1 sample also completely lost the N₂ adsorption step forthe filling of mesopores after the hydrothermal treatment. Regarding thestability of the KIT-1 sample, we conclude that KIT-1 has some thermalstability (better than MCM-41, but poorer than MSU-G). However, likeMCM-41, the hydrothermal stability of KIT-1 is very poor and greatlyinferior to MSU-G, as illustrated in Example 6.

EXAMPLE 6

The following examples were prepared to test the thermal andhydrothermal stabilities of the product of Example 2. The same procedureas described above for Examples 5 through 6 was employed for testing thestability of Example 2.

The product exhibited the same N₂ adsorption-desorption isotherms (FIG.8) without any significant change after the hydrothermal treatment at100° C. for 56 hours. After calcination at 1000° C. for 4 hours, theproduct exhibited two diffraction lines (FIG. 9) that are consistentwith an undulated lamellar structure.

The sample still showed a step in the N₂ adsorption isotherm for thefilling of mesopores between P/P_(o) at 0.2 and 0.3 (FIG. 8). The porevolume of the sample (0.31 cm³/g) only decreased by 25% respective tothat of calcined sample at 650° C. for 4 hours (0.42 cm³/g). Thus, theproduct of Example 2 was found to be superior in thermal andhydrothermal stability among the all previously reported mesoporoussilica mesostructures.

EXAMPLE 7

This example describes another preparation art for the incorporated Alcenters into the framework of an Example 2 silica by post-synthesisreaction of the mesostructure in the absence of template.

One gram of the air-dried and non-calcined product of Example 2 wasmixed with 100 milliliters of EtOH, stirred and refluxed for 1 hour. Theproduct was then filtered and washed with another portion of EtOH (100milliliters). The above washing procedure was repeated twice and thefiltered product was air-dried at 100° C. overnight. The solventextraction led to the removal of more than 95% of the template, whichwas confirmed by C, H, N elemental analysis and ¹³C MAS NMR. Aluminationwas conducted by heating a 0.5 gram of ethanol-extracted product in 25milliliters of 0.1 M aqueous solution of sodium aluminate in a tightlysealed flask. The flask was immersed in an oil bath at 60° C. for 1hour. The sample was filtered, washed with water, and calcined in air at620° C. for 4 hours. Elemental analysis for the Si/Al ratio wasperformed by inductively coupled plasma emission spectroscopy. The Si/Alratio of the final product was 11.7. The XRD pattern of the finalproduct exhibited a d₀₀₁ reflection centered at 58±1 Å. The SBET of thissample is 365 m²/g. ²⁷Al MAS NMR spectra of as-synthesized and calcinedExample 2 only exhibit a resonance at 53 ppm relative to 1.0M aqueousaluminum nitrate for tetrahedral Al sites (FIG. 10). This indicates thatthe alumination of MSU-G silica materials can be easily accomplished.

EXAMPLE 8–11

The following examples describe the preparation art of incorporated Tiand Al sites into framework of mesostructured silicas from Example 2 bypostsynthesis reaction in the presence of surfactant template in theframework. The molar ratio of metal to silicon in the final compositionwas 2% mole.

The same preparation art described in Example 1 through 3 was employed.An appropriate amount of metal source was added to the as-synthesizedsilica materials in its mother liquor. The resultant mixture was stirredfor 20 minutes and heated again for 48 hours at 100° C. After theautoclave was cooled to room temperature, the product was filtered,washed with water and ethanol, and air-dried. The template was removedthrough calcination in air at 650° C. for 4 hours. The metal sources andspecific amounts of metal source used in each particular exampletogether with the XRD patterns, BET surface areas, HK pore sizedistributions and pore wall thicknesses of the calcined product aresummarized in Table 2.

TABLE 2 Amount HK BET of pore Surface Wall Template d₀₀₁ size areathickness Example Formula of metal source used (g) (Å) (Å) (m²/g) (Å) 8Ti[OCH(CH₃)₂]₄ 0.14 58.1 32 450 26.1 9 Al(NO₃)₃ 0.19 59.6 34 468 25.6 10Al[C₂H₅CH(CH₃)O]₃ 0.12 59.6 34 444 25.6 11 NaAlO₂ 0.04 58.9 34 452 24.9²⁷Al MAS NMR spectra of as-synthesized and calcined product of Examples9 through 10 exhibit the high intensity peak at 53 ppm corresponding totetrahedral Al species with the low intensity peak at 0 ppmcorresponding to octahedral Al species. In contrast, the ²⁷Al MAS NMRspectra of Example 11 exhibited mainly a single peak at around 53 ppm.

EXAMPLES 12–17

The following examples illustrate the ability of extended geminisurfactants with larger alkyl chains between the two amino groups,(e.g., C_(n)H_(2n+1)NH(CH₂)_(m)NH₂, abbreviated as C °_(n-m-0), where;n=10, 12, 14 and m=3, 4) to act as templating agents for mesostructureformation in the manner of the present invention. These extended geminisurfactants were synthesized by previously described procedures (F. W.Short, E. F. Elslager, A. M. Moore, M. J. Sullivan and F. H. Tendick, J.Am. Chem. Soc., 80, 223, (1958)).

Solutions of C °_(n-m-0) were prepared as in the manner of thepreparation art of Examples 1 through 3. Si(OC₂H₅)₄ in the appropriateamount was added at once to the surfactant solution so that theSi:surfactant molar ratio was 10:1. The remainder of the synthesisprocedure was identical to the preparation art described in Examples 1through 3. The products after calcination at 650° C. exhibited XRDpatterns, BET surface areas, HK pore size distributions and pore wallthickness as described in Table 3.

TABLE 3 Amount of HK BET Template Template d₀₀₁ pore size Surface areaExample formula used (g) (Å) (Å) (m²/g) 12 C^(o) ₁₀₋₃₋₀ 1.34 39.1 30 65013 C^(o) ₁₂₋₃₋₀ 1.51 54.2 37 461 14 C^(o) ₁₄₋₃₋₀ 1.68 62.0 43 380 15C^(o) ₁₀₋₄₋₀ 1.43 48.0 32 614 16 C^(o) ₁₂₋₄₋₀ 1.60 53.9 34 465 17 C^(o)₁₄₋₄₋₀ 1.76 78.9 46 574

EXAMPLE 18

This example describes a preparation art for introducing functionalizedorganosilane moieties into the framework of MSU-G silicas by reaction ofthe lamellar silica framework with hydrolyzable organosilanes.

One gram of the as-synthesized product obtained in Example 2 silica wasextracted with hot ethanol to remove the surfactant and then dried undervacuum at 100° C. The dried, surfactant-free mesostructure was thenrefluxed with one gram of 3-mercaptopropyltrimethoxy-silane in twentyfive milliliters of dry toluene for 48 h. The functionalized product wasthen filtered, washed several times with toluene followed by EtOH, andsubject to Soxhlet extraction over EtOH for 18 h in order to removeresidual (ungrafted) organo silane. This product was dispersible inorganic solvents, indicating that the surface was made hydrophobicthrough grafting reaction of the surface silanol groups of the silicaframework with the organosilane. The XRD pattern of the functionalizedderivative gave a d₀₀₁ XRD peak near 57 Å, indicating the retention ofthe lamellar framework structure after function.

EXAMPLE 19

This Example illustrates the assembly of a MSU-G silica composition inthe presence of a gemini amine surfactant C °₁₂₋₂₋₀ and a co-surfactantJeffamine D-400, an alpha,omega propylene oxide diamine. Many otherco-surfactant may be used in place of the Jeffamine co-surfactant,including 1, 3, 5-trimethylbenzene, alkyl monoamines, polyethyleneoxide-based surfactants, and the like.

The surfactant mixture was prepared by adding 0.43 gram of C °₁₂₋₂₋₀ and1.75 gram of Jeffamine D-400 in thirty five milliliters of deionized H₂Oand five milliliters of ethanol, affording a C °₁₂₋₂₋₀:Jeffamine D-400molar ratio of 1.0:2.3. The resultant mixture was stirred at roomtemperature for 20 h until a milky solution was obtained. Si(OC₂H₅)₄ wasadded at once in the appropriate amount so that the Si:surfactant molarratio was 4:1 as in the preparation art of Examples 1 through 3. Theremainder of the synthesis was identical to the preparation artdescribed in Examples 1 through 3. The XRD pattern of the calcinedproduct exhibited a d₀₀₁ reflection centered at 50.2 Å. The SBET surfacearea of this sample was 422 m²/g. The ²⁷Si MAS NMR spectrum ofas-synthesized Example 19 exhibited two lines with relative intensitiescorresponding to a Q⁴/Q³ ratio of 9.4. A TEM image of this product (FIG.11) revealed a folded ribbon-like hierarchical structure for several ofthe fundamental particles comprising this product. Some particles alsoadopt an onion-like structure wherein composite spheres are formedthrough the concentric nesting of smaller and smaller silica spheres,one within another. Each concentric silica sphere is composed of asingle silica nanolayer that has closed upon itself to form a sphere.Channels between the concentric silica spheres provide frameworkmesopores for adsorption and chemical transformation (catalysis) ofguest molecules.

It is intended that the foregoing description be only illustrative andthat the present invention be limited only by the hereinafter appendedclaims.

1. A lamellar mesoporous inorganic oxide and silica composition, whereinthe inorganic oxide is other than silica, wherein the composition wasderived from a mesoporous silica composition without the inorganic oxidecomposition containing an electrically neutral amine surfactant, whereinthe surfactant is of the formula:RNH(CH₂)_(y)NHR¹ wherein y is 1 to 4, R is an alkyl moiety containing 10to 20 carbon atoms and R₁ is selected from the group consisting ofhydrogen, methyl, ethyl and (CH₂)_(m)NH₂ wherein m is 1, 2, 3 or 4 inmesopores, which surfactant has been removed from the silica compositionwhich silica composition without the inorganic oxide was then treatedpost-synthesis of the mesoporous silica composition with one or more ofan inorganic oxide forming compound of an inorganic element and thesurfactant and then the treated silica composition was heated to formthe inorganic oxide over and on silica composition so that the inorganicoxide and silica composition is lamellar and mesoporous, wherein theinorganic element is selected from the group consisting of B, Al, Ga,Fe, Co, Mn, Cr, Ge, Ti, V, Ni, Sn, Sb, Zr, W, Mo, Ca, Cu, Pb, In, Nb,Sr, and Zn.
 2. The composition of claim 1 wherein cross-linking of SiO₄tetrahedra in the silica to four adjacent silicon sites (Q⁴) and tothree adjacent silicon sites (Q³) corresponds to a Q⁴/Q³ ratio of atleast
 5. 3. The composition of claim 1 with at least one x-raydiffraction line corresponding to a basal spacing of 4 to 10 nm.
 4. Thecomposition of claim 1 wherein the surfactant has the formula:C_(n)H_(2n+1)NH(CH₂)₂NH₂ where n is an integer between 8 and
 20. 5. Thecomposition of claim 1 wherein a particle morphology of the silicacomposition without the inorganic oxide forming compound is vesicular,bowlshaped, tube-shaped, of an onion layer morphology, or foldedribbon-shaped with a diameter between about 10 and 1400 nm and with ashell thickness between about 2.0 nm and 200 nm, and wherein the shellthickness is comprised of between about 1 and about 50 nanolayers. 6.The composition of claim wherein the inorganic oxide and silicacomposition is functionalized by reaction with an organosilane selectedfrom the group consisting of X₃SiR, X₂SiR₂, XSiR₃ and mixtures thereofwhere X is a hydrolyzable moiety and R is an organic moiety whichcontains an organic functional group.
 7. A lamellar mesoporous inorganicoxide and silica composition derived from a mixed mesoporous silicacomposition and an inorganic element oxide forming compound applied witha surfactant post-synthesis of the mesoporous silica composition overthe mesoporous silica composition wherein the surfactant is of theformula:RNH(CH₂)_(y)NHR¹ wherein y is 1 to 4, R is an alkyl moiety containing 10to 20 carbon atoms and R¹ is selected from the group consisting ofhydrogen, methyl, ethyl and (CH₂)_(m)NH₂ wherein m is 1, 2, 3 or 4 andheated so as to be over the silica composition and so that the inorganicoxide and silica composition is lamellar and mesoporous, wherein theinorganic element is selected from the group consisting of B, Al, Ga,Fe, Co, Mn, Cr, Ge, Ti, V, Ni, Sn, Sb, Zr, W, Mo, Ca, Cu, Pb, In, Nb,Sr, and Zn.
 8. The composition of claim 7 with at least one x-raydiffraction line corresponding to a basal spacing of 4 to 10 nm.